Surface modification of ceramic particles is an important way to improve the dielectric properties of ceramic/polymer composites . In this work, H2O2 and silane coupling agent KH550 were used to modify the surface of BaTiO3(BT) ceramic particles twice. Modified BaTiO3/PVDF(M-BT/PVDF) films were prepared by a simple solution blending and casting process. The results show that the use of H2O2 and silane coupling agent KH550 can enhance the interface bonding of BT and PVDF effectively, and thus improve the dielectric constant of the composites. The dielectric constant of the composites reaches to 36 when the volume fraction of BT is 60%, which is six times of pristine PVDF matrix, and the dielectric loss is 5%.